Authors:F. Rey, O. Chamorro, F. Martín Gil, and J. Martín Gil
The thermal stability of selected straight-chain (C6-C14) esters of fatty acids has been studied by TG-DTG and DTA analysis. In DTG, a peak is detected between 84° and 125° C followed
by a main effect in the range 105°–215°C, whereas in DTA only an exothermic peak appears in the range of 126.5° to 187°C (onset
temperatures). The temperatures of these effects have been related with ignition points, molecular weights and boiling points.
The characteristics of melting and recrystallization of the above fatty acid methyl esters and those with carbon numbers between
C14 and C24 have been established by DSC along the melting range between −83° and 50°C. Polymorphism appears in caproic, heptanoic, palmitic
and stearic acid methyl esters.
Authors:M. Cirri, F. Maestrelli, S. Furlanetto, and P. Mura
Natural crystalline (α-, β-, γ-) and amorphous derivative (hydroxypropyl-β- and methyl-β) cyclodextrins were selected as potential
carriers for obtaining, through a co-grinding technique, a stable activated amorphous form of glyburide with improved dissolution
properties. Differential scanning calorimetry (DSC) was used to investigate solid-state modifications of the drug induced
by co-grinding with the selected carriers in a high energy vibrational micro-mill. X-ray powder diffraction and FTIR spectroscopy
were employed as additional techniques to support DSC data. Equimolar drug : cyclodextrin physical mixtures were co-ground
for different times (up to 60 min) at constant vibration frequency (24 Hz). A progressive drug amorphization with increasing
grinding time was observed in all binary systems, but, interestingly, different degrees of sensitivity to the mechanical-chemical
activation were evident. In fact, blends with natural cyclodextrins, despite the initial higher crystallinity than those with
the amorphous derivatives, required the same or shorter co-grinding times (60 min) to achieve complete drug amorphization.
Stability studies indicated no appreciable drug recrystallization in co-ground products after 4 months storage in sealed containers
at 25°C or 1 month at 25°C and 75% RH. No stability differences were detected between products with natural or derivative
cyclodextrins. The results accounted for the suitability of cyclodextrin co-grinding technique to obtain and stabilize glyburide
in the activated amorphous form.
Authors:S. Romero, P. Bustamante, B. Escalera, M. Cirri, and P. Mura
Differential scanning calorimetry (DSC), supported by hot stage microscopy, IR spectroscopy and X-ray powder diffractometry,
was used to investigate the characteristics of the solid phases of mefenamic, niflumic, and flufenamic acids and of paracetamol,
before and after equilibration with saturated solutions in different solvents. Mixtures of Lewis base (dioxane and ethyl acetate)
and amphiprotic solvents (ethanol and water) were prepared for evaluating the influence of both nature and polarity of the
solvents. Solid-state analysis performed on the original samples (commercial products) made it possible to establish that
paracetamol, mefenamic acid and flufenamic acid were in their respective Form I. No polymorphic modifications are known for
niflumic acid. Paracetamol, niflumic and mefenamic acids did not show any change after equilibration with the various solvents
or solvent mixtures, regardless of their different chemical nature. In contrast, DSC, IR and X-ray analyses revealed the partial
recrystallization of flufenamic acid into its polymorphic Form III in solid phases at equilibrium with ethanol, ethyl acetate
and their blends, as well as in dioxane-water mixtures containing 30 to 100% dioxane and in ethanol-water mixtures with a
water content less than 50%.
We studied thermal transitions and physical stability
of oil-in-water emulsions containing different milk fat compositions, arising
from anhydrous milk fat alone (AMF) or in mixture (2:1 mass ratio) with a
high melting temperature (AMF–HMT) or a low melting temperature (AMF–LMT)
fraction. Changes in thermal transitions in bulk fat and emulsion samples
were monitored by differential scanning calorimetry (DSC) under controlled
cooling and reheating cycles performed between 50 and –45C (5C
min–1). Comparison between bulk fat samples
and emulsions indicated similar values of melting completion temperature,
whereas initial temperature of fat crystallization (Tonset)
seemed to be differently affected by storage temperature depending on triacylglycerols
(TAG) composition. After storage at 4C, Tonset
values were very similar for emulsified and non-emulsified AMF–HMT blend,
whereas they were lower (by approx. 6C) for emulsions containing AMF
or mixture of AMF–LMT fraction. After storage at –30C, Tonset values of re-crystallization
were higher in emulsion samples than in bulk fat blends, whatever the TAG
fat composition. Light scattering measurements and fluorescence microscopic
observations indicated differences in fat droplet aggregation-coalescence
under freeze-thaw procedure, depending on emulsion fat composition. It appeared
that under quiescent freezing, emulsion containing AMF–LMT fraction
was much less resistant to fat droplet aggregation-coalescence than emulsions
containing AMF or AMF–HMT fraction. Our results indicated the role of
fat droplet liquid-solid content on emulsion stability.
Authors:Z. Mohd Ishak, P. Shang, and J. Karger-Kocsis
The polymerization of a cyclic butylene terephthalate
(CBT) oligomer was studied as a function of temperature (T=200
and 260C, respectively) by modulated DSC (MDSC). The first heating was
followed by cooling after various holding times (5, 15 and 30 min) prior to
the second heating which ended always at T=260C.
This allowed us to study the crystallization and melting behavior of the resulting
polybutylene terephthalate (PBT), as well. In contrary to the usual belief,
the CBT polymerization is exothermic and the related process is superimposed
to that of the CBT melting. The melting behavior of the PBT was affected by
the polymerization mode (performed below or above the melting temperature
of the PBT product) of the CBT. Annealing above the melting temperature of
PBT yielded a product featuring double melting. This was attributed to the
presence of crystallites with different degrees of perfection. The crystals
perfection which occurred via recrystallization/remelting was manifested by
a pronounced exothermic peak in the non-reversing trace.
Isotactic polypropylene (iPP) was crystallized using temperature modulation in a differential scanning calorimeter (DSC) to thicken the crystals formed on cooling from the melt. A cool-heat modulation method was adopted for the preparation of the samples under a series of conditions. The effect of modulation parameters, such as temperature amplitude and period was monitored with the heating rate that followed. Thickening of the lamellae as a result of the crystallization treatment enabled by the cool-heat method lead to an increase in the peak melting temperature and the final traces of melting. For instance, iPP melting peak shifted by up to 3.5°C with temperature amplitude of 1.0°C while the crystallinity was increased from 0.45 (linearly cooled) to 0.53. Multiple melting endotherms were also observed in some cases, but this was sensitive to the temperature changes experienced on cooling. Even with a slower underlying cooling rate and small temperature amplitudes, some recrystallization and reorganization occurred during the subsequent heating scan. The crystallinity was increased significantly and this was attributed to the crystal perfection that occurred at the crystal growth surface. In addition, temperature modulated differential scanning calorimetry (TMDSC) has been used to study the melting of iPP for various crystallization treatments. The reversing and non-reversing contribution under the experimental time scale was modified by the relative crystal stability formed during crystallization. Much of the melting of iPP was found to be irreversible.
Authors:Nathaniel B. Zuckerman, Maxim Shusteff, Philip F. Pagoria, and Alexander E. Gash
The secondary high explosive 2,6-diamino-3,5-dinitropyrazine-1-oxide, or LLM-105, has been synthesized using a commercially available flow microreactor system. Investigations focused on optimizing flow nitration conditions of the cost effective 2,6-diaminopyrazine-1-oxide (DAPO) in order to test the feasibility and viability of flow nitration as a means for the continuous synthesis of LLM-105. The typical benefits of microreactor flow synthesis including safety, tight temperature control, decreased reaction time, and improved product purity all appear to be highly relevant in the synthesis of LLM-105. However, the process does not provide any gains in yield, as the typical 50—60% yields are equivalent to the batch process. A key factor in producing pure LLM-105 lies in the ability to eliminate any acid inclusions in the final crystalline material through both a controlled quench and recrystallization. The optimized flow nitration conditions, multigram scale-up results, analyses of sample purity, and quenching conditions for purity and crystal morphology are reported.
In mineralogical research differential thermal analysis can be applied as either a single or a combined method for three purposes:1.for the qualitative identification of minerals and the (semi-)quantitative determination of the components of rocks and soils,2.for the characterization of crystal-physical and crystal-chemical properties, including the study of kinetics and the determination of thermodynamic data, phase and reaction equilibria,3.for special petrogenetic investigations concerning the interrelation of mineralogical properties with the formation, decomposition or recrystallization of minerals.
Authors:Dariusz Bochenek, Małgorzata Płońska, Julian Dudek, and Zygmunt Surowiak
Results of investigations on selected ceramic ferroics and multiferroics by TA method were presented. The authors of the work
used the thermal analysis both to optimize a process of producing the ceramic ferroics and multiferroics and to examine phase
transitions in that type of materials. In the case of synthesis of the ferroics and multiferroics as a result of sintering
of a mixture of simple oxides, the TA method enables to determine the optimum synthesis temperature and temperatures of re-crystallization
and disintegration of compounds and solid solutions. In the case of the sol–gel method, temperatures of dehydratization, burning
of an organic phase, and crystallization of an amorphous powder formed from the residual gel were determined by the TA method.
The TA method was also used to control a process of compacting and sintering the powders at high temperatures (Ts > 1,200 K), thus in a process of ceramic specimen formation. During rapid phase transitions, the ferroelectric specimens
of a first type emit (in the cooling process) or absorb (in the heating process) so called latent heat of the phase transitions.
On the DTA courses, it may be manifested in a form of exo- or endothermic peaks in the Curie temperature area (TC). The test materials included the ferroelectric ceramics of composition x/65/35 PLZT (ferroic for x < 9 at%) and mixed bismuth oxide layered perovskites (M-BOLP) of composition Bi5TiNbWO15 with <m> = 1.5 and the mutliferroic Pb(Fe1−xNbx)O3 ceramics (PFN) and Bi5TiFeO15 (BTF).
A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χc, χMA, χRA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared
by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly
heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow
the devitrification of the rigid amorphous fraction to be examined.
We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief
heating above this lower endotherm and immediately quenching in LN2-cooled glass beads, the glass transition temperature and χRA decrease substantially, χMA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification
of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χRA to increase, and χMA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal
reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid
Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid
amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show
the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξA) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of
some of the RAF leads to the broadening of the glass transition region and shift of Tg.